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Methanesulfonyl chloride → 3-(4-chloromethyl-5-ethyl-thiazol-2-yl)-1-cyclohexylmethyl-7-methoxy-1H-indole

HRID 644043
Notizen
Druckvorschau

Reaktionsgleichung

Reaktionsgleichung von HRID 644043
CS([Cl:5])(=O)=O.[CH:6]1([CH2:12][N:13]2[C:21]3[C:16](=[CH:17][CH:18]=[CH:19][C:20]=3[O:22][CH3:23])[C:15]([C:24]3[S:25][C:26]([CH2:31][CH3:32])=[C:27]([CH2:29]O)[N:28]=3)=[CH:14]2)[CH2:11][CH2:10][CH2:9][CH2:8][CH2:7]1.C(N(C(C)C)CC)(C)C>ClCCl>[Cl:5][CH2:29][C:27]1[N:28]=[C:24]([C:15]2[C:16]3[C:21](=[C:20]([O:22][CH3:23])[CH:19]=[CH:18][CH:17]=3)[N:13]([CH2:12][CH:6]3[CH2:11][CH2:10][CH2:9][CH2:8][CH2:7]3)[CH:14]=2)[S:25][C:26]=1[CH2:31][CH3:32]
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Komponenten

5

Edukt 3

HCID 31297Methanesulfonyl chlorideHCID 81531DiisopropylethylamineHCID 68697587[2-(1-cyclohexylmethyl-7-methoxy-1H-indol-3-yl)-5-ethyl-thiazole-4-yl]-methanol

Produkt 1

HCID 686948583-(4-chloromethyl-5-ethyl-thiazol-2-yl)-1-cyclohexylmethyl-7-methoxy-1H-indoleAusbeute 49,4 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 6344
Dichloromethane
Lösungsmittel

Versuchsvorschrift

Lithium borohydride (200 mg, 9.09 mmol) was added portionwise to a mixture of 2-(1-cyclohexylmethyl-7-methoxy-1H-indol-3-yl)-5-ethyl-thiazole-4-carboxylic acid ethyl ester (490 mg, 1.15 mmol) and tetrahydrofuran (5 ml) under ice-water cooling and the resulting mixture was stirred at 0° C. for 2 h. The reaction mixture was quenched with aqueous hydrochloric acid (2 M; 2 ml), and the aqueous layer extracted with dichloromethane (2×100 ml). The organic layers were combined, dried over magnesium sulfate, and concentrated in vacuo to yield the crude product. Silica gel column chromatography eluting with 66% ethyl acetate in heptane gave crude [2-(1-cyclohexylmethyl-7-methoxy-1H-indol-3-yl)-5-ethyl-thiazole-4-yl]-methanol (210 mg). This material was used in the next step without further purification. Methanesulfonylchloride (90 μl, 1.16 mmol) was added to a mixture of [2-(1-cyclohexylmethyl-7-methoxy-1H-indol-3-yl)-5-ethyl-thiazole-4-yl]-methanol (210 mg, 0.547 mmol), diisopropylethylamine (150 μl, 0.91 mmol) and dichloromethane (5 ml) under ice-water cooling and the resulting mixture was allowed to warm to room temperature slowly. Stirring was continued for 22 hours. The reaction mixture was quenched with 5% aqueous sodium carbonate (2 ml), and the aqueous layer extracted with dichloromethane (2×10 ml). The organic layers were combined, dried over magnesium sulfate, and concentrated in vacuo to yield the crude product. Flash column chromatography eluting with 10% acetone in n-heptane afforded 3-(4-chloromethyl-5-ethyl-thiazol-2-yl)-1-cyclohexylmethyl-7-methoxy-1H-indole (109 mg). Dimethylamine (2.2 M solution in tetrahydrofuran; 0.50 ml) was added to a mixture of 3-(4-chloromethyl-5-ethyl-thiazol-2-yl)-1-cyclohexylmethyl-7-methoxy-1H-indole (38 mg, 0.095 mmol), potassium carbonate (16 mg, 0.113 mmol) and sodium iodide (14 mg, 0.095 mmol) in acetonitrile (2 ml). The mixture was subjected to microwave irradiation for 5 min at 160° C., then partitioned between dichloromethane (20 ml) and 5% aqueous sodium carbonate (5 ml). The aqueous layer was extracted with dichloromethane (10 ml) and the combined organic layers were dried over magnesium sulfate and concentrated in vacuo. The resulting oil was dissolved in diethyl ether, then hydrogen chloride (1M solution in diethyl ether; 3 ml) was added to the solution. The resulting mixture was concentrated in vacuo to afford the title compound as a 1:1 hydrochloride salt (40 mg, 0.089 mmol). 1H NMR (400 MHz, CD3OD) δ 1.04-1.15 (2H, m), 1.16-1.30 (3H, m), 1.43 (3H, t, J 7.0), 1.55-1.78 (5H, m), 1.82-1.92 (1H, m), 3.05 (8H, m), 3.99 (3H, s), 4.33 (2H, d, J 7), 4.62 (2H, s), 6.91 (1H, d, J 8.0), 7.29 (1H, t, J 8.0), 7.62 (1H, d, J 8), 8.30 (1H, s). EIMS: m/z 412.3 [M+H]+, 367.0.

Aufarbeitung

  1. customThis material was used in the next step without further purification
  2. customThe reaction mixture was quenched with 5% aqueous sodium carbonate (2 ml)
  3. extractionthe aqueous layer extracted with dichloromethane (2×10 ml)
  4. dry with materialdried over magnesium sulfate
  5. concentrationconcentrated in vacuo
  6. customto yield the crude product
  7. washFlash column chromatography eluting with 10% acetone in n-heptane

Quellen und Nachweise

ORD-Eintrag
ord-a979530a1f9b42a6a754bf5de29376f8
Quelldatensatz
uspto-grants-2010_04
DOI
10.6084/m9.figshare.5104873.v1
Patentnummer
US07700634B2

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